TW200301294A - Electro-conductive composition, electro-conductive coating and method for producing the coating - Google Patents
Electro-conductive composition, electro-conductive coating and method for producing the coating Download PDFInfo
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- TW200301294A TW200301294A TW091137359A TW91137359A TW200301294A TW 200301294 A TW200301294 A TW 200301294A TW 091137359 A TW091137359 A TW 091137359A TW 91137359 A TW91137359 A TW 91137359A TW 200301294 A TW200301294 A TW 200301294A
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- silver
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- conductive film
- conductive composition
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Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/14—Conductive material dispersed in non-conductive inorganic material
- H01B1/16—Conductive material dispersed in non-conductive inorganic material the conductive material comprising metals or alloys
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/20—Conductive material dispersed in non-conductive organic material
- H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/24—Electrically-conducting paints
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/09—Use of materials for the conductive, e.g. metallic pattern
- H05K1/092—Dispersed materials, e.g. conductive pastes or inks
- H05K1/095—Dispersed materials, e.g. conductive pastes or inks for polymer thick films, i.e. having a permanent organic polymeric binder
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/30—Assembling printed circuits with electric components, e.g. with resistor
- H05K3/32—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits
- H05K3/321—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits by conductive adhesives
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
- H05K2203/11—Treatments characterised by their effect, e.g. heating, cooling, roughening
- H05K2203/1157—Using means for chemical reduction
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
- H05K2203/12—Using specific substances
- H05K2203/125—Inorganic compounds, e.g. silver salt
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/10—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
- H05K3/105—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern by conversion of non-conductive material on or in the support into conductive material, e.g. by using an energy beam
Abstract
Description
玖、發明說明 (發明說明應敘明：發明所屬之技術領域、先前技術、内容、實施方式及圓式簡單說明） 【發明所屬之技術領域】 技術領域 本發明係有關於一種作為導電性糊、導電性塗料、導 電性黏著劑等使用之導電性組成物，與使用該導電性組成 物之導電性覆膜之形成方法及藉由該形成方法得到之導電 性覆膜，且係可充分提高所得到之導電性覆膜之導電性並 可得到逼近金屬銀之導電性者。 【】 背景技術 以往之導電性糊係以銀糊為代表，該銀糊係於層狀之 銀粒子中摻合混煉丙稀g請脂、醋酸乙婦_樹脂等之熱可 塑性樹脂、環氧樹脂、聚_脂等之熱硬化性樹脂等所構 成之黏結劑、有機溶劑、硬化劑、觸媒等而得到者。 該銀糊係廣泛地使用作為各種電子機器、電子零件、 電子電路等之導電性黏著劑、導電性塗料等。又，亦被使 用作為藉由網目印刷等將該銀糊印刷於聚對苯二甲酸乙二 8曰等之塑膠薄膜上並形成電路之撓性印刷電路板、鍵盤與 各種開關等之印刷電路板中。 該銀糊之使用方法係藉由各種塗布裝置塗布於對象物 並以吊溫乾燥或加熱至150°C而作成導電性覆膜來進行。 ^其次，依此所得到之導電性覆膜之體積電阻率雖依照 製膜條件而有不同、然而於1G-4〜nem之範圍者了 相李父於金屬銀之體積電阻率1·6χ1〇—6Ω· cm為1〇〜1〇〇倍 玖、發明說明 之值，始終比不上金屬銀之導電性。 由此種習知銀糊所構成之導電性覆膜之導電性低之原 因係由於下述理由所致’即：由銀糊所得到之導電性覆膜 内僅銀粒子之一部分物理性地接觸而接觸點少；具有於接 觸點之接觸阻力；於-部分銀粒子間殘存黏結劑，該黏結 劑阻礙銀粒子之直接接觸等。 將銀糊塗 作為改善此種銀糊之導電性低落之方法有说明 Description of the invention (the description of the invention should state: the technical field to which the invention belongs, the prior art, the content, the embodiments, and a brief explanation of the invention) [Technical Field to which the invention belongs] TECHNICAL FIELD The present invention relates to a conductive paste, The conductive composition used for conductive coatings, conductive adhesives, and the like, the method for forming the conductive coating using the conductive composition, and the conductive coating obtained by the forming method can fully improve the The conductivity of the obtained conductive film can be similar to that of metallic silver. [Background Art] A conventional conductive paste is represented by a silver paste, which is a thermoplastic resin, epoxy resin, epoxy resin, epoxy resin, epoxy resin, and the like mixed and mixed with layered silver particles. It is obtained by a binder, an organic solvent, a hardener, a catalyst and the like made of a thermosetting resin such as a resin and a polyester. This silver paste is widely used as a conductive adhesive, a conductive paint, and the like in various electronic devices, electronic parts, and electronic circuits. In addition, it is also used as a flexible printed circuit board for printing a silver paste on a plastic film of polyethylene terephthalate and the like by screen printing, and a printed circuit board for a keyboard and various switches. in. The method of using the silver paste is to coat the object with various coating devices and dry it at a hanging temperature or heat it to 150 ° C to form a conductive film. ^ Secondly, although the volume resistivity of the conductive film obtained according to this varies according to the film formation conditions, it is in the range of 1G-4 to nem. The volume resistivity of the father Li to metal silver is 1.6 × 1 —6Ω · cm is 10 ～ 100 times the value of the invention description, and it is always inferior to the conductivity of metallic silver. The reason why the conductivity of the conductive coating film composed of such a conventional silver paste is low is because of the following reasons, that is, only a part of the silver particles in the conductive coating film obtained from the silver paste are physically contacted and come into contact. There are few points; there is contact resistance at the contact point; a binder remains between the-part of the silver particles, and the binder hinders the direct contact of the silver particles. The silver paste is used as a method for improving the conductivity of the silver paste.
布於對象物並加熱至，燃燒除去黏結劑，同時使銀 粒子溶融絲粒子熔合而作成同樣地連續之金屬銀覆膜者 10 。依此得到之導電性覆膜之體積電阻率為101Ω· 有接近金屬銀之體積電阻率之導電性。 然而，該方法卻具有僅限於對象物為耐高溫加熱之玻 璃、陶瓷、搪瓷等之耐熱性材料之缺點。 又，於上述撓性電路板中，於該電路板形成之電路之 15線寬被要求盡量地縮小。然而，由於習知銀糊所使用之銀It is applied to an object and heated to the point where it is burned to remove the binder, and at the same time, the silver particles are melted and the wire particles are fused to form the same continuous metallic silver film 10. The volume resistivity of the conductive film thus obtained was 101Ω. The conductivity was close to the volume resistivity of metallic silver. However, this method has the disadvantage that it is limited to heat-resistant materials such as glass, ceramics, and enamel, which are resistant to high-temperature heating. Further, in the above-mentioned flexible circuit board, the 15-line width of a circuit formed on the circuit board is required to be reduced as much as possible. However, due to the silver
粒子係粒徑1〜100_之層狀，因此，在原理上並無法印 刷小於層狀銀粒子粒徑之線寬之電路。 且，雖然要求要縮小電路之線冑，但卻同時要求具有 充刀之導電丨生，因應該要求則必須大大地增加電路之厚度 2〇。然而，若增加電路之厚度則製膜困難，產生電路本身之 可撓性亦大幅降低之問題。 依此，本發明之目的係在於即使不依照高溫之製膜條 件亦可付到與金屬銀匹敵之低體積電阻率、高導電性之導 電性覆膜’且得到於形成撓性電路板等之電路時可充分地 8 ^ 2ϋ〇3〇Ι：94 玖、發明說明 縮小其電路之線寬且毋須增加其厚度之導電性組成物。 【發明内容】 發明之揭示 - 為了達成前述目的，本發明之導電性組成物係由粒+ 狀銀化合物與還原劑所構成。該粒子狀銀化合物係可使帛 . 氧化銀、碳酸銀、醋酸銀等。該粒子狀銀化合物之平均粒 徑為 0.01 〜ΙΟμπι。 本發明之導電性覆膜之形成方法係塗布、加熱導電性 鲁 組成物方法。 本發明之導電性覆膜係藉由前述形成方法而得到者， 且銀粒子係相互地熔合。又，該導電性覆膜係塗布前述導 電性組成物並以150〜20(rc加熱3〇分鐘而得到者，又， 若以V電性覆膜之體積電阻率（Q · cm)為w，且以其比重 為X，則滿足下述式（1)。 WS — 1.72x10-6χχ+2·3χ10-5…(1) 再者’該導電性覆膜係塗布前述導電性組成物並以 · 150〜200 C加熱30分鐘而得到者，又，若以存在於導電性 復膜最表面之1 〇pmx 1 〇pm之表面積之1⑼以上之空隙 - 數（個）為Y，且以加熱溫度（1)為z，則滿足下述式（2)。 Υ< -46.08 · Ζ+ 10112---(2) 粒子狀銀化合物係藉由於還原劑之共存下之加熱而輕 易地還原為金屬銀粒子，且因該還原反應時之反應熱所析 出之金屬銀粒子熔融且相互地熔合而形成高導電性之金屬 銀覆膜。因此，所得到之導電性覆膜係發揮與金屬銀匹敵 9 玖、發明說明 之導電性。 圖式簡單說明 第1圖係由本發明之導電性組成物所得到之導電性覆 膜表面之掃瞄式電子顯微鏡照片。 第2圖係由以往之銀糊所得到之導電性覆膜表面之掃 瞄式電子顯微鏡照片。 第3圖係顯示具體例中導電性覆膜之體積電阻率與比 重之關係之圖。 第4圖係顯示具體例中導電性覆膜之表面空隙數與加 熱溫度之關係之圖。Particles have a layered shape with a particle size of 1 to 100 mm. Therefore, in principle, it is not possible to print a circuit with a line width smaller than the layered silver particle size. In addition, although it is required to reduce the wiring of the circuit, at the same time, it is required to have sufficient conduction of the knife. Therefore, the thickness of the circuit must be greatly increased according to the requirements. However, if the thickness of the circuit is increased, it is difficult to form a film, and the problem is that the flexibility of the circuit itself is greatly reduced. Accordingly, the object of the present invention is to provide a conductive film having a low volume resistivity and high conductivity, which is comparable to that of metallic silver, even if it does not comply with high temperature film forming conditions, and to obtain a flexible circuit board or the like When the circuit is sufficient, the conductive composition can reduce the line width of the circuit sufficiently without increasing its thickness. [Summary of the Invention] Disclosure of the Invention-In order to achieve the foregoing object, the conductive composition of the present invention is composed of a granular + silver compound and a reducing agent. This particulate silver compound is capable of making 帛. Silver oxide, silver carbonate, silver acetate, and the like. The average particle diameter of the particulate silver compound is 0.01 to 10 μm. The method for forming the conductive film of the present invention is a method of coating and heating a conductive composition. The conductive film of the present invention is obtained by the aforementioned forming method, and the silver particles are fused to each other. The conductive coating is obtained by coating the conductive composition and heating it at 150 to 20 (rc for 30 minutes). If the volume resistivity (Q · cm) of the V electrical coating is w, When the specific gravity is X, the following formula (1) is satisfied: WS — 1.72x10-6χχ + 2 · 3χ10-5… (1) Furthermore, “the conductive film is coated with the aforementioned conductive composition and is subjected to“ It is obtained by heating at 150 ~ 200 C for 30 minutes, and if the number of voids-number (number) that exists on the surface of the conductive composite film with a surface area of 10 pmx 10 pm or more is Y, and the heating temperature ( 1) is z, which satisfies the following formula (2): Υ <-46.08 · Zn + 10112 --- (2) The particulate silver compound is easily reduced to metallic silver particles by heating under the coexistence of a reducing agent. Moreover, the metallic silver particles precipitated by the heat of reaction during the reduction reaction are melted and fused with each other to form a highly conductive metallic silver coating. Therefore, the obtained conductive coating is comparable to metallic silver. The conductivity of the invention is illustrated in the drawing. The first diagram is a diagram of the conductivity of the conductive composition obtained from the conductive composition of the present invention. Scanning electron microscope photograph of the surface. Figure 2 is a scanning electron microscope photograph of the surface of a conductive film obtained from a conventional silver paste. Figure 3 is a volume resistivity of the conductive film in a specific example. The relationship between the specific gravity and the specific gravity. Figure 4 shows the relationship between the number of surface voids and the heating temperature of the conductive film in the specific example.
【實施方式；J 發明之較佳實施形態 以下詳細說明本發明。 本發明之導電性組成物所使用之粒子狀銀化合物係具 有藉由於還原劑存在下之加熱而還原並成為金屬銀之性質 之固體粒子狀之化合物。 該粒子狀銀化合物之具體例可列舉如氧化銀、碳酸銀 、醋酸銀等。該等亦可混合2種以上來使用。該粒子狀銀 化合物除了可將工業上所生產者直接或分級來使用之外， 亦可於粉碎後分級再使用。又，亦可使用藉由後述液相法 或氣相法所得到者。 遠粒子狀銀化合物之平均粒徑係在0.01〜ΙΟμιη之範圍 内而還原反應條件可依照如加熱溫度、還原劑之還原力 等而適當地加以選擇。特別是若使用平均粒徑為〇·5μιη以 玖、發明說明 下之粒子狀銀化合物，則還原反應速度增快且較為理想。 又，平均粒徑〇·5μηι以下之粒子狀銀化合物係藉由銀 化合物與其他化合物間之反應所生成者，例如，可藉由在 攪拌下於硝酸銀水溶液中滴下氫氧化鈉等之鹼性水溶液並 5使其反應而得到氧化銀之液相法來製造。此時，係以於溶 * 液中添加分散安定劑來防止所析出之粒子狀銀化合物之凝 集者為佳。該液相法中，藉由使銀化合物濃度、分散安定 劑濃度等變化而可控制粒子徑。 · 又，為了得到平均粒徑0·1μηι以下之微粒子之粒子狀 10銀化合物，可使用於氣相中加熱齒化銀與氧並進行熱氧化 而合成氧化銀之氣相法。 由於本發明所使用之還原劑係還原前述粒子狀銀化合 物者，因此，係以還原反應後之副生成物為氣體或揮發性 高之液體且不會殘留於所生成之導電性覆膜内者為佳。此 15種還原劑之具體例可列舉如：乙二醇、一縮二乙二醇、二 縮三乙二醇、乙二醇二乙酸醋等之i種或2種以上之混纟 · 物。 該還原劑之使用量係相對於粒子狀銀化合物丨莫耳為 · 20莫耳以下者為佳，較佳者為〇·5〜1〇莫耳，且以}〜5莫 、 2〇耳尤佳。若考慮反應效率或因加熱之揮發，則以添加比等 莫耳更多一些者為佳，然而，即使添加超過最大之2〇莫耳 ’该部分亦為白費。 又，分散或溶解粒子狀銀化合物與還原劑並得到液狀 之導電性組成物係使用分散介質。該分散介質係使用水、 11 ^ 2UJ30i：94 玖、發明說明 甲醇、乙醇、丙醇等之醇類、異佛樂萌、ί!品醇、二縮三 乙二醇單丁鍵、乙二醇單丁鍵醋酸等之有機溶劑。 又，若前述還原劑係以液狀來分散粒子狀銀化合物者 ’則還原劑可兼作分散介質，該還原劑係有乙二醇、-縮 5 二乙二醇等。 該分散介質之種類選擇及其使用量係依照粒子狀銀化 物或製膜條件而不同，例如於網目印刷中依照刷版之網目 粗度或印刷圖案之精細度等而可適當地調整以進行最適當 之製膜。 又可添加为散劑而使平均粒子徑1 以下之粒子狀 銀化物良好地分散，並以防止粒子狀銀化物之二次凝集者 為佳。該分散劑係使用經丙基纖維素、聚乙婦四氮。比略嗣 、聚乙烯醇等，且其使用量係相對於粒子狀銀化合物100 重量份而為0〜300重量份。 本發明之導電性組成物係將前述粒子狀銀化合物與還 原劑分散·溶解於分散介質者。又，亦可依需要添加分散 背J。在此所使用之粒子狀銀化合物之平均粒徑並不限於粒 徑小者，若為〇·〇1〜1〇μηι之範圍則不會有特別的問題，且 即使為Ιμηι以上之粒子，還原反應亦可平順地進行。 又，該導電性組成物之黏度係依照製膜條件而不同， 然而’例如於網目印刷時係以3〇〜3〇〇泊為佳。 X»亥導電性組成物之使用方法，即，本發明之導電性覆 膜之形成方法係可於藉由適當裝置將該導電性組成物塗布 於對象物後僅將其加熱者。加熱溫度係因還原劑之存在而 12 2u〇3〇iC94 玖、發明說明 為140〜160°C，加熱時間為10秒〜12〇分。 另’當然要對對象物之表面進行清潔。 依此得到之本發明之導電性覆膜_，粒子狀銀化合物 ， 還原且業已還原之金屬銀粒子相互地熔合而構成連續之金 5 屬銀薄覆膜。 - 第1圖係顯示依此得到之導電性覆膜之一例子之掃瞄 式電子顯微鏡照片。由該照片顯然亦可理解構成金屬銀之 連續覆膜者。 Φ 因此，本發明之導電性覆膜之體積電阻率係顯示3〜 1〇 8Χΐ〇—6Ω · cm之值，且為與金屬銀之體積電阻率同程度之 專級。 又，由於粒子狀銀化合物之平均粒徑為〇〇1〜1〇μπι , 因此可將利用該導電性組成物進行基材之印刷而形成之電 路之線寬作成ΙΟμιη以下，且由於電路本身之導電性極高 15 ,因此亦毋須增加電路之厚度。故，電路之形成容易且電 路本身之可撓性亦高。 鲁 再者’由於用以形成導電性覆膜之加熱溫度係14〇〜 160 c即足夠，因此亦可適用於耐熱性低之塑膠薄膜等之對 _ 象物，且可形成高導電性覆膜，同時亦不會導致對象物之 _ 2〇 熱劣化。 再者，由於所得到之導電性覆膜之體積電阻率極低， 因此即使覆膜之厚度作成極薄亦可得到充分之導電性。覆 膜厚度係可相對於習知導電性糊而就與體積電阻率降低相 抵之部分來削薄。例如，使用5x10—5Ω · cm之銀糊時，若 13 ^ 200301294 玖、發明說明 要求厚度50μηι之電路規格，則藉由本發明實現3χ1〇—% • cm之體積電阻率，可作成3μπι之厚度。 又，由於所得到之導電性覆膜之基材側之面係呈現富 有金屬銀光澤之鏡面，因此，玻璃、塑膠薄膜等透明基材 5之裏面或自基材所剝離之導電性覆膜之基材側表面係作為 * 反射率高之鏡子而可使用於家庭用、工業用等之用途中， 例如可使用於雷射裝置之共振器之反射鏡等。 又，有關由本發明之導電性組成物所得到之導電性覆 · 膜係顯然成立下述關係。 即，針對將刖述導電性組成物塗布於玻璃板等基板並 以150〜2GG°C加熱3G分鐘所得到之導電性覆制定其體 積電阻率與其比重且嘗試求取該等之關係，若以導電性覆 膜之體積電阻率.㈣為W，且以其比重為χ，則顯然 滿足前述式（1)。 因此，藉由規定該比重以使所得到之導電性覆膜之體 積電阻率為小於式⑴之值，則可得到良好之導電性覆膜。 · 又，藉由掃瞄式電子顯微鏡來觀察並求取存在於同樣 地得到之導電性覆膜最表面之平均單位面積之空隙數，且 嘗試求取其空隙數與加熱溫度間之關係，若以存在於㈣ . 2〇性覆膜最表面之10μηιχ1〇μιη之表面積之咖肺以上之空 隙數（個）為Υ’且以加熱溫度（。〇為ζ，則顯然滿足前述式 (2)。 由該關係可知’為了形成空隙少之良好之導電性覆膜 ，則可適當地控制加熱溫度，且藉由18〇〜綱。C之加熱， 14 坎、發明說明 高之導電性覆膜 可知到空隙數少之導電性 以下係顯示具體例。 (例1) -銀，谷解於50ml之離子交換水中，並辞 備於其中溶解有〇〇5〜 冰、 · g之羥丙基纖維素（分散劑）之;^ '搜掉下於该水溶液中滴下〇·9〜5ml之1M氫氧化金 水溶液並持續㈣1G〜3G分鐘，作減化㈣浮液。 、：接者’藉由甲醇將氧化銀洗淨2〜5次並除去剩餘之離 匕後|加並混合〇()6〜ig之乙二醇（還原劑）且製 造出本發明之糊狀導電性組成物。[Embodiment; J Preferred Embodiment of the Invention] The present invention will be described in detail below. The particulate silver compound used in the conductive composition of the present invention is a solid particulate compound having the property of being reduced to metal silver by heating in the presence of a reducing agent. Specific examples of the particulate silver compound include silver oxide, silver carbonate, and silver acetate. These may be used by mixing two or more kinds. The particulate silver compound can be used directly or classified by industrial producers, and can also be classified and used after pulverization. It is also possible to use one obtained by a liquid phase method or a gas phase method described later. The average particle diameter of the far-particle silver compound is in the range of 0.01 to 10 µm, and the reduction reaction conditions can be appropriately selected in accordance with, for example, the heating temperature, the reducing power of the reducing agent, and the like. In particular, when a particulate silver compound having an average particle diameter of 0.5 μm or less and described in the description of the invention is used, the reduction reaction speed is faster and more desirable. In addition, a particulate silver compound having an average particle diameter of 0.5 μm or less is produced by a reaction between a silver compound and another compound. For example, an alkaline aqueous solution such as sodium hydroxide can be dropped into an aqueous silver nitrate solution while stirring. Then, it is reacted to produce silver oxide by a liquid phase method. In this case, it is preferable to add a dispersion stabilizer to the solution to prevent aggregation of the precipitated particulate silver compound. In this liquid phase method, the particle diameter can be controlled by changing the silver compound concentration, the dispersion stabilizer concentration, and the like. In addition, in order to obtain particulate 10 silver compounds with fine particles having an average particle diameter of 0.1 μm or less, the gas phase method can be used to synthesize silver oxide by heating dental silver and oxygen in the gas phase and thermally oxidizing them. Since the reducing agent used in the present invention is for reducing the aforementioned particulate silver compound, the by-products after the reduction reaction are gas or highly volatile liquid and do not remain in the generated conductive film. Better. Specific examples of these 15 kinds of reducing agents include i, or a mixture of two or more kinds of ethylene glycol, diethylene glycol, diethylene glycol, ethylene glycol diacetate, and the like. The amount of the reducing agent used is preferably 20 mol or less relative to the particulate silver compound. Mol is less than 20 mol, and more preferably 0.5 to 10 mol. good. If the reaction efficiency or volatilization due to heating is taken into consideration, it is better to add more than equal moles. However, even if the amount exceeds 20 moles, the portion is in vain. A dispersion medium is used to disperse or dissolve the particulate silver compound and the reducing agent to obtain a liquid conductive composition. The dispersion medium uses water, 11 ^ 2UJ30i: 94 玖, the description of the alcohols such as methanol, ethanol, propanol, etc., isophorone, bis! Alcohol, triethylene glycol monobutylene bond, ethylene glycol Organic solvents such as monobutyl acetic acid. If the reducing agent is a liquid state in which the particulate silver compound is dispersed, the reducing agent may also serve as a dispersing medium. Examples of the reducing agent include ethylene glycol and 5-glycol. The selection of the type of the dispersion medium and its amount of use are different according to the particulate silver compound or film-forming conditions. For example, in the screen printing, the mesh thickness of the printing plate or the fineness of the printing pattern can be appropriately adjusted to optimize the Proper film formation. It may be added as a powder to disperse the particulate silver compounds having an average particle diameter of 1 or less, and it is preferable to prevent secondary aggregation of the particulate silver compounds. As this dispersant, propylcellulose and polytetrazine were used. The ratio is slightly larger, polyvinyl alcohol, and the like, and the usage amount thereof is 0 to 300 parts by weight based on 100 parts by weight of the particulate silver compound. The conductive composition of the present invention is one in which the aforementioned particulate silver compound and a reducing agent are dispersed and dissolved in a dispersion medium. Moreover, a dispersion | distribution back J may be added as needed. The average particle diameter of the particulate silver compound used here is not limited to those having a small particle diameter, and if it is in the range of 0.001 to 10 μm, there will be no particular problem, and even if the particle size is 1 μm or more, reduction The reaction can also proceed smoothly. In addition, the viscosity of the conductive composition varies depending on the film forming conditions, but it is preferably 30 to 300 poise, for example, when screen printing is performed. The method of using the X »Hi conductive composition, that is, the method for forming the conductive film of the present invention, is to apply the conductive composition to an object by an appropriate device and then heat it only. The heating temperature is based on the presence of a reducing agent. 12 2u03iC94 发明, the description of the invention is 140 ~ 160 ° C, and the heating time is 10 seconds ~ 120 minutes. In addition, of course, the surface of the object must be cleaned. The conductive coating film of the present invention thus obtained, the particulate silver compound, and the reduced and reduced metal silver particles are fused with each other to form a continuous gold thin film of silver. -Figure 1 is a scanning electron microscope photograph showing an example of the conductive film thus obtained. It is apparent from this photograph that those who constitute the continuous coating of metallic silver. Φ Therefore, the volume resistivity of the conductive film of the present invention shows a value of 3 to 108 × 6-6 Ω · cm, and is the same level as the volume resistivity of metallic silver. In addition, since the average particle diameter of the particulate silver compound is 0.001 to 10 μm, the line width of a circuit formed by printing the base material using the conductive composition can be made 10 μm or less, and because of the circuit itself, The conductivity is extremely high, so there is no need to increase the thickness of the circuit. Therefore, the circuit is easy to form and the circuit itself is highly flexible. "Lu Zaiyi's" is sufficient because the heating temperature used to form the conductive film is 14 ~ 160 c, so it can also be applied to objects with low heat resistance such as plastic films, and can form high conductive films At the same time, it will not cause _20 thermal degradation of the object. Furthermore, since the volume resistivity of the obtained conductive coating film is extremely low, sufficient conductivity can be obtained even if the thickness of the coating film is made extremely thin. The thickness of the film can be reduced by a portion which is inferior to the decrease in volume resistivity with respect to the conventional conductive paste. For example, when using a silver paste of 5x10-5Ω · cm, if 13 ^ 200301294 发明, the description of the invention requires a circuit specification with a thickness of 50μm, the volume resistivity of 3x10-% • cm can be achieved by the present invention, and the thickness can be made 3μm. In addition, since the surface on the substrate side of the obtained conductive film is a mirror surface rich in metallic silver gloss, the inside of the transparent substrate 5 such as glass or plastic film or the conductive film peeled from the substrate is The substrate-side surface can be used as a mirror with high reflectance and can be used in domestic and industrial applications. For example, it can be used as a mirror for a resonator of a laser device. Further, it is apparent that the following relationship is established regarding the conductive coating film obtained from the conductive composition of the present invention. That is, the volume resistivity and specific gravity of the conductive coating obtained by coating the above-mentioned conductive composition on a substrate such as a glass plate and heating it at 150 to 2 GG ° C for 3 G minutes are determined, and an attempt is made to determine the relationship between these. The volume resistivity of the conductive film. ㈣ is W, and its specific gravity is χ, it is obvious that the aforementioned formula (1) is satisfied. Therefore, by setting the specific gravity so that the volume resistivity of the obtained conductive film is smaller than the value of formula (i), a good conductive film can be obtained. · Observe and calculate the number of voids per unit area on the outermost surface of the conductive film obtained in the same way with a scanning electron microscope, and try to find the relationship between the number of voids and the heating temperature. When the number of voids (number) above the lungs with a surface area of 10 μηι × 10 μιη present on the outermost surface of the 性 20 film is Υ ′ and the heating temperature (.0 is ζ), the aforementioned formula (2) is obviously satisfied. From this relationship, it can be seen that, in order to form a good conductive film with few voids, the heating temperature can be appropriately controlled, and a high conductive film with a temperature of 14 ° C and a description of the invention can be obtained by heating at 180 ° C. The following shows a specific example of the conductivity with a small number of voids. (Example 1) -Silver was dissolved in 50 ml of ion-exchanged water, and it was interpreted that hydroxypropylcellulose (0.5 to 1 g of ice) was dissolved therein ( Dispersant); ^ 'Search and drop the 0.9M ~ 5ml 1M gold hydroxide aqueous solution in this aqueous solution and continue to G1G ~ 3G minutes, as a sublimation ㈣ floating solution. ：: Receiver' will be oxidized by methanol After silver wash 2 ~ 5 times and remove the remaining dagger Square fit () 6~ig of ethylene glycol (reducing agent) and create a paste made of a conductive composition of the present invention.
^藉由網目印刷將該導電性組成物於厚度…咖之聚對 苯二曱酸乙二S旨薄膜上形成厚度5〜1()师之圖案後，於妙 爐中以15(TC將其加熱3〇分〜3小時。 15^ The conductive composition was patterned by screen printing to a thickness of 5 ~ 1 () on a poly-ethylene terephthalate film with a thickness of 15 ° C, and then was formed in a magic furnace at 15 ° C Heat for 30 minutes to 3 hours. 15
/斤得到之圖案之體積電阻率係3〜6x 10、.cm，藉 由掃目田式電子顯微鏡觀察表面時，如帛i圖所示，自氧化 銀還原析出之銀粒子間係熔合接合。 (例2) 為了加以比較’使用市售之銀糊（藤倉化成（股）製造商 品名「FA — 353」），並藉由網目印刷將該銀糊於厚度 20 〇.lmm之聚對苯二甲酸乙二醋薄膜上形成厚度5〜1〇μηι2 圖案後，於烘爐中以15(TC將其加熱3〇分鐘。 所得到之圖案之體積電阻率係4χ 1〇-5Ω · cm ,藉由掃 瞄式電子顯微鏡觀察表面時，銀層間僅為接觸之狀熊。 又，使用市售之其他銀糊（朝日化學研究所製造）並同 15 玖、發明說明 樣地形成圖案時，其體積電阻率係3χ ι〇—5Ω·⑽，藉由掃 目苗式電子顯微鏡觀察表面時，係如第2圖之掃猫式電子顯 微鏡照片中所示，銀層間僅為接觸之狀熊。 (例3) 於作成恒重之玻璃基板上塗布厚度5〜1〇阿之前述例 1中之導電性組成物，且於烘爐中以15(rtx3G》、細。c X 30刀之條件將其加熱’測定所得到之導電性覆膜之體積 電阻率與比重並求取其關係時，得到如第3圖所示圖之結 果。 由該圖求取回歸方程式時，可求出前述式（1)。 又，針對同樣地製作之導電性覆膜，藉由掃猫式電子 顯微鏡觀察其表面並算出存在於其最表面之空隙數，且求 取该空隙數與加熱溫度之關係時，可得到第4圖圖所示之 結果。 由該圖求取回歸方程式時，可得到前述式（2)。 (例4) 使用100重量份之氧化銀來作為粒子狀銀化合物且使 用75重畺份之乙二醇來作為還原劑，且改變氧化銀之平均 粒徑而形成導電性覆膜，並測定其體積電阻率。又，藉由 掃瞎式電子顯微鏡來觀察銀粒子間有無熔合。 於基材上使用厚度0.1mm之聚對苯二甲酸乙二酯薄膜 並藉由網目印刷於其上形成厚度5〜1 〇 之圖案，以 150°C加熱30分至3小時。 平均粒徑Ο.ΟΙμηι之氧化銀係藉由氣相法來製作，平均 10〜 玖、發明說明 粒徑°·1〜一者係藉由液相法來製作，平均粒徑 15μΙΏ者係將市售品分級來使用。 結果係顯示於表1。The volume resistivity of the pattern obtained is 3 to 6 x 10, .cm. When the surface is observed by a Sumida electron microscope, as shown in Figure IX, the silver particles reduced and precipitated from silver oxide are fused and bonded. (Example 2) For comparison, a commercially available silver paste (brand name "FA — 353" manufactured by Fujikura Kasei Co., Ltd.) was used, and the silver paste was applied to polyparaphenylene diene with a thickness of 20 0.1 mm by screen printing. After a 5 to 10 μm 2 pattern was formed on the ethylene formate film, it was heated in an oven at 15 ° C. for 30 minutes. The volume resistivity of the obtained pattern was 4 × 10-5 Ω · cm. When scanning the surface with a scanning electron microscope, the silver layers were only contact bears. When using other commercially available silver paste (manufactured by the Asahi Chemical Research Institute) and forming a pattern in the same manner as described in the invention, the volume resistance was 15 The rate is 3 × ω—5Ω · ⑽. When the surface is observed with a scanning electron microscope, as shown in the photograph of the scanning cat electron microscope in Figure 2, the silver layers are only contact-like bears. (Example 3) ) On the glass substrate made of constant weight, apply the conductive composition of the aforementioned Example 1 with a thickness of 5 to 10 angstroms, and heat it in an oven at 15 (rtx3G ", fine. C X 30 knives' When measuring the volume resistivity and specific gravity of the obtained conductive film and determining the relationship, The result is shown in the graph shown in Fig. 3. When the regression equation is obtained from the graph, the above-mentioned formula (1) can be obtained. The conductive film prepared in the same manner was observed with a scanning electron microscope. When the number of voids existing on the surface is calculated and the relationship between the number of voids and the heating temperature is obtained, the result shown in Fig. 4 can be obtained. When the regression equation is obtained from this graph, the aforementioned formula ( 2). (Example 4) Using 100 parts by weight of silver oxide as the particulate silver compound and using 75 parts by weight of ethylene glycol as the reducing agent, and changing the average particle diameter of the silver oxide to form a conductive film, The volume resistivity was measured. Furthermore, the presence or absence of fusion between the silver particles was observed by a scanning electron microscope. A 0.1-mm-thick polyethylene terephthalate film was used on the substrate and printed on the screen. A pattern having a thickness of 5 to 10 was formed and heated at 150 ° C for 30 minutes to 3 hours. The silver oxide having an average particle size of 0.01 μm was prepared by a gas phase method, and the average particle size was 10 to 玖. ~ One is made by liquid phase method, average Those having a particle size of 15 μl were used by classifying commercially available products. The results are shown in Table 1.
使用平均粒徑〇.25_之氧化銀來作為粒子狀銀化合物 臭還原劑之種類及其組合而形成導電性覆膜，並測 疋其體積電阻率。又，藉由掃瞒式電子顯微鏡來觀察銀粒 子〗有”、、熔合。相對於100重量份之氧化銀，將還原劑全 部重量摻合75重量份。 於基材上使用厚度〇.lmm之聚對苯二甲酸乙二酯薄膜 ’並藉由網目印刷於其上形成厚度5〜10_之圖案，以 15〇°C加熱30分至3小時。 結果係顯示於表2。 17 玖、發明說明A silver oxide having an average particle diameter of 0.25 mm was used as the kind of particulate silver compound and the type and combination of odor reducing agents to form a conductive film, and its volume resistivity was measured. In addition, the silver particles were observed by a concealed electron microscope, and fusion was performed. 75 weight parts of the total weight of the reducing agent was mixed with 100 weight parts of the silver oxide. A thickness of 0.1 mm was used on the substrate. A polyethylene terephthalate film was formed on the film by screen printing to a thickness of 5 to 10 mm, and heated at 150 ° C for 30 minutes to 3 hours. The results are shown in Table 2. 17 发明, Invention Description
測試編號 還原劑之種類 乙二醇 •縮二乙二醇 —-------- 乙一醇二乙酸酉旨 體積電阻率 (Ω · cm) 銀粒子間有無熔t 由 # ^--——_ 衣 之結果可知，即使改變還原劑之種類、組合，Types of test number reducing agents: ethylene glycol and diethylene glycol —-------- Glycol Diacetate Purpose Volume resistivity (Ω · cm) Is there any melting between silver particles? # ^ --— —_ The result of clothing shows that even if the type and combination of reducing agents are changed,
體積電阻率亦為. A ”、 Ω · Cm之專級，可形成實際使用上無 問題之導電性覆膜。 ^ 5 (例6) 之種類及其組合而形成導電性覆 。又，藉由掃瞄式電子顯微鏡來 改變粒子狀銀化合物 膜，並測定其體積電阻率 觀察銀粒子間有無熔合。 還原劑係使用乙二醇，且相對於重量份之粒子狀 10銀化合物全部重量而摻合75重量份。 於基材上使用厚度（Umm之聚對苯二甲酸乙二醋薄膜 ’並藉由網目印刷於其上形成厚度5〜1〇帅之圖案:以 150°C加熱30分至3小時。 ' 結果係顯示於表3及表4。 18 15 UJ30i294 玖、發明說明 表3 測試編號 14 15 16 17 18 粒子狀銀化合物 碳酸銀 碳酸銀 碳酸銀 醋酸銀 醋酸銀 平均粒徑（μπι) 0.1 1.5 5 5 10 體積電阻率 4x 10'6 1 7.5χ 1〇~6 ) 8x 10~6 > 6·5χ 1〇 一 6 8x 1〇'6 (Ω · cm) 7x 1〇~6 ( lx 10一5 C 1·2χ 10 一5 ( lx 10~5 1 3·4χ 1〇一5 銀粒子間有無溶合 有 有 有 有 有 表4 測5式編號 19 20 21 22 23 24 25 粒子狀銀化 合物 氧化銀 氧化銀 氧化銀 氧化銀 碳酸銀 氧化銀 氧化銀 平均粒徑 (μπι) 0.25 0.25 0.25 5 0.35 0.25 0.25 摻合比 (wt% ) 50 70 50 60 50 33 50 粒子狀銀化 合物 碳酸銀 碳酸銀 醋酸銀 醋酸銀 醋酸銀 碳酸銀 碳酸銀 平均粒徑 0.35 5 5 5 5 0.35 5 摻合比 (wt% ) 50 30 50 40 50 33 25 粒子狀銀化 合物 — — 醋酸銀 醋酸銀 平均粒徑 (um) 一 — — 5 5 摻合比 (wt% ) 一 — — 34 25 體積電阻率 (Ω · cm) 4x 10'6 1 6.7x 10'6 7x 1〇-6 1 8.3χ 1〇~6 6.2χ 1〇~6 1 8.5χ 1〇~6 8χ 10-6 1 1.2χ1(Γ5 5.4χ 10'6 1 9.1χ 10~6 4.2χ 1〇-6 1 7χ 10~6 7·9χ 1〇 -6 1 1.lx 10 一5 銀粒子間 有無溶合 有 有 卜有 有 有 有 有 由表3及表4之結果可知，即使使氧化銀、碳酸銀、 醋酸銀或其組合改變，體積電阻率亦為1〇 —6Ω· cm之等級 可形成實際使用上無問題之導電性覆膜。 如前所述，若藉由本發明之導電性組成物，則可得到 ‘ _30i294 坎、發明說明 - 導電性極高之導電性覆膜。又’由於該導電性覆膜之形成 係藉由較低溫之加熱即可充分地進行，因此可使用耐触 - 低之塑膠等來料基材。再者，藉由該導電性組成物形& . 電路時，可充分地縮小電路之線寬，且毋須增加其厚度。 . 5 產業上之利用領域 · 本發明之導電性組成物係可使用作為導電性糊、導電 性塗料、導電性黏著劑等。又，亦可使用於撓性印刷電路 板等之印刷配線板之電路形成用中。再者，該導電性覆膜 鲁 亦可作為高反射率之反射薄膜使用。 10 【囷式簡單說明】 第1圖係由本發明之導電性組成物所得到之導電性覆 膜表面之掃瞄式電子顯微鏡照片。 第2圖係由以往之銀糊所得到之導電性覆膜表面之掃 目苗式電子顯微鏡照片。 15 第3圖係顯示具體例中導電性覆膜之體積電阻率與比 重之關係之圖。 · 第4圖係顯示具體例中導電性覆膜之表面空隙數與加 熱溫度之關係之圖。 、 【圖式之主要元件代表符號表】 (無） 20The volume resistivity is also A., Ω · Cm, which can form a conductive coating without any problems in practical use. ^ 5 (Example 6) types and combinations to form a conductive coating. Also, by The scanning electron microscope was used to change the granular silver compound film, and the volume resistivity was measured to observe the fusion between the silver particles. The reducing agent was ethylene glycol and was blended with respect to the total weight of the particulate 10 silver compound in parts by weight. 75 parts by weight. Use a thickness (Umm of polyethylene terephthalate film 'on the substrate and form a pattern with a thickness of 5 to 10 by screen printing: heating at 150 ° C for 30 minutes to 3 Hours. 'Results are shown in Tables 3 and 4. 18 15 UJ30i294 玖, Description of Invention Table 3 Test No. 14 15 16 17 18 Granular silver compound silver carbonate silver carbonate silver carbonate silver acetate average particle size (μπι) 0.1 1.5 5 5 10 Volume resistivity 4x 10'6 1 7.5χ 1〇 ~ 6) 8x 10 ~ 6 > 6.5χ 10〇 6 8x 1〇'6 (Ω · cm) 7x 1〇 ~ 6 (lx 10 -5 C 1 · 2χ 10-5 (lx 10 ~ 5 1 3 · 4χ 10.5 Table 4 Test 5 Formula Number 19 20 21 22 23 24 25 Particle silver compound silver oxide silver oxide silver oxide silver carbonate silver oxide silver oxide silver oxide average particle size (μπι) 0.25 0.25 0.25 5 0.35 0.25 0.25 Blending ratio (wt %) 50 70 50 60 50 33 50 Particulate silver compound silver carbonate silver carbonate silver acetate silver acetate silver acetate silver carbonate silver carbonate average particle diameter 0.35 5 5 5 5 0.35 5 Blending ratio (wt%) 50 30 50 40 50 33 25 granular silver compound—silver acetate average particle diameter of silver acetate (um) one — 5 5 blending ratio (wt%) one — 34 25 volume resistivity (Ω · cm) 4x 10'6 1 6.7x 10 '6 7x 1〇-6 1 8.3χ 1〇 ~ 6 6.2χ 1〇 ~ 6 1 8.5χ 10 ~ 6 8χ 10-6 1 1.2χ1 (Γ5 5.4χ 10'6 1 9.1χ 10 ~ 6 4.2χ 1 〇-6 1 7χ 10 ~ 6 7 · 9χ 1〇-6 1 1.lx 10 -5 Whether the silver particles are fused or not With or without the presence or absence The results in Tables 3 and 4 show that even with silver oxide , Silver carbonate, silver acetate, or a combination thereof, and the volume resistivity is also in the range of 10-6 Ω · cm, which can form a conductive film without problems in practical use. As described above, if the conductive composition of the present invention is used, a '__30i294' can be obtained. Explanation of the Invention-A conductive film having extremely high conductivity. In addition, since the formation of the conductive film can be sufficiently performed by heating at a relatively low temperature, a base material such as a touch-resistant plastic can be used. Furthermore, when the conductive composition is shaped & the circuit, the line width of the circuit can be sufficiently reduced without increasing its thickness. . 5 Industrial applications · The conductive composition of the present invention can be used as a conductive paste, a conductive coating, a conductive adhesive, and the like. It can also be used for circuit formation of printed wiring boards such as flexible printed circuit boards. Moreover, the conductive film Lu can also be used as a reflective film with high reflectance. 10 [Brief description of the formula] Fig. 1 is a scanning electron microscope photograph of the surface of a conductive film obtained from the conductive composition of the present invention. Fig. 2 is a scanning electron microscope photograph of the surface of a conductive film obtained from a conventional silver paste. 15 Figure 3 is a graph showing the relationship between the volume resistivity and the specific gravity of the conductive film in a specific example. • Figure 4 is a graph showing the relationship between the number of surface voids of the conductive film and the heating temperature in the specific example. [Symbol table of the main components of the diagram] (None) 20
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-
2002
- 2002-12-25 JP JP2003557004A patent/JP4156522B2/en not_active Expired - Fee Related
- 2002-12-25 KR KR1020047010045A patent/KR100951726B1/en active IP Right Grant
- 2002-12-25 CN CNB028259599A patent/CN100428368C/en not_active Expired - Lifetime
- 2002-12-25 EP EP07001372A patent/EP1775734B1/en not_active Expired - Lifetime
- 2002-12-25 US US10/500,124 patent/US20040259007A1/en not_active Abandoned
- 2002-12-25 DE DE60221433T patent/DE60221433T2/en not_active Expired - Lifetime
- 2002-12-25 DE DE60237174T patent/DE60237174D1/en not_active Expired - Lifetime
- 2002-12-25 WO PCT/JP2002/013502 patent/WO2003056574A1/en active IP Right Grant
- 2002-12-25 EP EP02793374A patent/EP1460644B1/en not_active Expired - Lifetime
- 2002-12-25 TW TW091137359A patent/TW588101B/en not_active IP Right Cessation
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2008
- 2008-02-07 JP JP2008027898A patent/JP2008177172A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| US20040259007A1 (en) | 2004-12-23 |
| WO2003056574A1 (en) | 2003-07-10 |
| TW588101B (en) | 2004-05-21 |
| DE60237174D1 (en) | 2010-09-09 |
| EP1460644B1 (en) | 2007-07-25 |
| EP1775734A2 (en) | 2007-04-18 |
| KR100951726B1 (en) | 2010-04-07 |
| CN100428368C (en) | 2008-10-22 |
| EP1775734A3 (en) | 2008-04-23 |
| EP1460644A4 (en) | 2005-03-16 |
| EP1460644A1 (en) | 2004-09-22 |
| JPWO2003056574A1 (en) | 2005-05-12 |
| DE60221433T2 (en) | 2008-04-10 |
| DE60221433D1 (en) | 2007-09-06 |
| EP1775734B1 (en) | 2010-07-28 |
| JP4156522B2 (en) | 2008-09-24 |
| CN1608296A (en) | 2005-04-20 |
| JP2008177172A (en) | 2008-07-31 |
| KR20040083071A (en) | 2004-09-30 |
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| MM4A | Annulment or lapse of patent due to non-payment of fees |